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Patented Mar. 16, 1943 Edgar C. Britten and 01 land, Mich., assignors Company, Midland, Mich.,

Michigan arence L. Moyle, Midto The Dow Chemical a corporation of No Drawing. Application February 6, 1941, Serial N0. 377,655

6 Claims. ('01. 260-613) This invention concerns mono-ethers of chloroalkyl acetals having the general formula:-

where R and R each represent a member of the group consisting of hydrogen and an alkyl radical containing not more than 3 carbon atoms and R" represents a member of the group consisting of monovalent aliphatic radicals and aromatic radicals.

, Examples of preferred compounds are those wherein R represents'the methyl radical, R. represents hydrogen, and R" represents a phenyl radical although R may also represent the ethyl, propyl, or butyl radicals, R may also represent an alkyl radical, and R" may also represent analiphatic radical and other aromatic radicals, such as those derived from hydroxy biphenyl, halophenols, alkyl phenols, phenol sulfonic acids, salicylic acid derivatives, hydroxy phenyl sulfones, hydroxy phenols, hydroxy aromatic ketones, etc.

The new mono-ethers of chloro-alkyl acetals are high boiling compounds with ya sweet odor.

They vary in color from colorless to pale yellow. The compounds have insecticidal properties. They may also be used as intermediates in the preparation of sulfites,,amines, sulfides, and esters by reaction of the remaining halogen with sodium sulfite, amines orammonia, sodium sulfide, and metallic salts of acids respectively.

The new compounds may be prepared by reaetmg sodium phenate or alcoholate with a. molar equivalent or more of a di-(beta-chloroalkyl) acetal at a temperature of approximately 50-l20 C. for 5-20 hours. A desirable temperature is that at which gentle reflux occurs. When the reaction is complete, water is added to dissolve the salt formed. The oil layer is then separated and distilled to produce the desired product.

The following examples illustrate a number of ways in which the principle of the invention may be employed, but are not to be construed as limiting the invention.

Example 1 A mixture of 81 grams (0.4 mol) of the sodium salt of 2-hydroxy-diphenyl and 149 grams (0.8 mol) of bis-beta-chloroethyl acetal was stirred and gently refluxed for 20 hours at 110 C. The salt formed was dissolved in 150 c. c. of water. The oil which separated was distilled 'to obtain 1-(2 chloroethoxy) 1-(2-(2-xenoxy) ethoxy) ethane having the formula:

CgHa

This compound is a pale yellow, slightly viscous liquid having a sweet odor. It has a boiling point or 212221 C. at 7 mm. pressure, a'specific gravity at 25/20 of 1.130, and a refractive index at 25 of 1.5718.

Example 2 A mixture of 79 grams (0.4 mol) of 2,4,6-trichloro phenol, 80 c. c. (0.4 mol) of a 20 per cent aqueous sodium hydroxide solution, and 149 grams (0.8 mol) of bis-beta-chloroethyl acetal was refluxed at 103105 C. for 10 hours. The resulting oil was washed with water and distilled. The product was 1-(2-chloroethoxy) -1- (2-(2,4,6-trichloro phenoxy) ethoxy) ethane, having the formula:

()lO-O-C mom-o-ouwrm-o-o molnol This compound is a pale yellow mobile liquid having a faint sweet odor. It has a boiling point of 199-201 C. at 6 mm. pressure, a specific gravity at 25/20 of 1.364, a refractive index at 25 of 1.5308, and an observed molecular refraction of 78.93 (ca1cu1ated=78.83).

Example 3 A mixture of 51.4 grams (0.4 mol) of parachlorophenol, 149 grams (0.8 mol) of bis-beta chloroethyl acetal, 80 c. c. (0.4 mol) of a 20 per cent aqueous sodium hydroxide solution was refluxed at 107 -l08 C. for 12 hours. The resulting oil was washed with water and distilled. The product was 1-(2-chloroethoxy) -1-(2-(4-chlorophenoxy) -ethoxy) -ethane, having the formula:

yellow mobile liquid a boiling C. at 6 mm. pressure, a speof 1.210, and a refractive This compound is a pale which crystallized on standing. It has point of l'l7"-179 cific gravity at 25l20 index'at 25 of 1.5172.

Example 4 A mixture of 88.6 grams (0.3 mol) of para-chlorophenol, 104 grams (0.6 mol) of bis-bete-chloroethyl formal, and 60 c. c. (0.3 mol) of a 20 per cent aqueous sodium hydroxide solution was refluxed at 110-119 C. for 6 hours. Thevoil layer was distilled to yield 1-(2-chloroethoxy) -1-(2-(4- chlorophenoxy)-ethoxy)-methane, having the formula:

The product is a pale yellow mobile liquid with a sweet sickening odor. It has a boiling point of 174-181 C. at 5.7 mm. pressure, a specific gravity at 25/20 of 1.24. and a refractive index at 25 of 1.522.

Example 5 A mixture of 32.4 grams (0.3 mol) oi. orthocresol, 104 grams (0.6 mol) of bis-beta-chloroethyl formal, and 60 0.0. (0.3 mol) of aqueous sodium hydroxide was refluxed at 109-110.5 C. for 6 hours. The oil layer was distilled to obtain 1-(2-chloroethoxy) -1-(2-(2 toloxy) ethoxy) -methane, having the formula:

O-o-omcm-o-cm-o-cmcmcx The product is a very pale yellow mobile liquid with a faint sweet odor. It has a boiling point of 160-165 C. at 6 mm. pressure, a specific gravity at 25/20 of 1.14, and a refractive index at 25 of 1.5082.

Example 6 n-CaHu-O-CHzCHe-O-CH-O-CHsCHrOl This compound is a colorless mobile oil with a boiling point of '-l30' C. at 13 mm. pressure,

a specific gravity at 25725 of 1.01, a refractive index at 25' of 1.4349, and an observed molecule refraction of 58.2 (oalculated=58.2).

Other mono-ethers of chloro-alkyl acetals of the present invention are'l-(z-chloropropoxyh 1-(2-p-bromophenoxyethoxy) butane, 1-(2-ch1oroethoxy) -1- (2-phenoxyethoxy) ethane, 1- (2- chloroethoxy) -1- (2 (4 carboxyphenoxy) ethoxy) ethane, etc.

We claim:

1. A mono-ether of a chloro-alkyl acetaLsaid compound having the general formula: Cl-CH:CH -0--( 3H- O=OH-CHf-O-R R i'l wherein R and R each represents a member 01' the group consisting of hydrogen and alkyl radicals containing not more than 3 carbon atoms and R" represents a member of the group consisting of monovalent aliphatic radicals and aromatic radicals.

2. A mono-ether of a chloro-alkyl acetal, said compound having the general formula:

ClCH:CH-O-CH-OCH-OR" n OH: R wherein R. represents a member of the group consisting of hydrogen and alkyl radicals containing not more than 3 carbon atoms and R" represents a member of the group consisting of monovalent aliphatic radicals and aromatic radicals.

3. A mono-ether of a chloro-alkyl acetal, compound having the general formula:

ci-om-cH,-0-cn-ocH.-cH,-0-R" said wherein R" represents a member of the group consisting of monovalent aliphatic radicals and aromatic radicals.

4; 1-(2-chloroethoxy) -1-(2-(2 xenoxy) ethoxy) ethane.

5. 1-(2-chloroethoxy) l (2 phenoxyethoxy) ethane.

6. 1-(2-chloroethoxy) 1-(2- (2,4,6 trichlorophenoxy)-ethoxy) ethane.

EDGAR C. BRITTON. CLARENCE L. MOYLE. 

